Fast-chargeable lithium battery

Abstract

Provided is a lithium secondary battery containing an anode, a cathode, a porous separator disposed between the anode and the cathode, an electrolyte, and a lithium ion reservoir disposed between the anode and the porous separator and configured to receive lithium ions from the cathode when the battery is charged and enable the lithium ions to enter the anode in a time-delayed manner, wherein the reservoir comprises a conducting porous framework structure having pores (pore size from 1 nm to 500 μm) and lithium-capturing groups residing in the pores, wherein the lithium-capturing groups are selected from (a) redox forming species that reversibly form a redox pair with a lithium ion; (b) electron-donating groups interspaced between non-electron-donating groups; (c) anions and cations wherein the anions are more mobile than the cations; or (d) chemical reducing groups that partially reduce lithium ions from Li.sup.+1 to Li.sup.+δ, wherein 0<δ<1.

Claims

1. A lithium secondary battery comprising an anode, a cathode, a porous separator disposed between said anode and said cathode, an electrolyte, and a lithium ion reservoir disposed between said anode and said porous separator and configured to receive lithium ions from said cathode through said porous separator when said battery is charged and enable said lithium ions to enter said anode in a time-delayed manner, wherein said lithium ion reservoir comprises an electron-conducting or lithium ion-conducting porous framework structure having pores, having a pore size from 1 nm to 500 μm, and said pores are impregnated with a compound including lithium-capturing groups residing in said pores, wherein said lithium ion-conducting porous structure comprises a polymer foam or polymer fabric having pore walls comprising a lithium ion-conducting polymer having a lithium ion conductivity from 10.sup.−8 to 10.sup.−2 S/cm when measured at 25° C., wherein said lithium-capturing groups are selected from (a) redox forming species that reversibly form a redox pair with a lithium ion when said battery is charged; (b) electron-donating groups interspaced between non-electron-donating groups; (c) anions and cations wherein the anions are more mobile than the cations; or (d) chemical reducing groups that partially reduce lithium ions from Li.sup.+1 to Li.sup.+δ, wherein 0<δ<1.

2. The lithium secondary battery of claim 1, wherein the lithium-capturing group is selected from a molecule having a core or backbone structure and at least a side group that contains an ionic or electron rich group; wherein the core or backbone structure contains an aryl, heterocycloalkyl, crown etheryl, cyclamyl, cyclenyl, 1,4,7-triazacyclononayl, hexacyclenyl, cryptandyl, naphtalenyl, antracenyl, phenantrenyl, tetracenyl, chrysenyl, tryphenylenyl, pyrenyl, pentacenyl, single-benzene or cyclic structure, double-benzene or bi-cyclic structure, or multiple-cyclic structure having 3-10 benzene rings and wherein the side group contains CO.sub.2H, CO.sub.2M.sup.1, CO.sub.2R, SO.sub.3H, SO.sub.3M.sup.1, PO.sub.3H.sub.2, PO.sub.3M.sup.1.sub.2, PO.sub.3M.sup.1H, PO.sub.4H.sub.2, PO.sub.4M.sup.1.sub.2, PO.sub.4M.sup.1H, PO.sub.4M.sup.2, C(O)NHOH, NH.sub.2, NHR, N(R).sub.2, NO.sub.2, COOR, CHO, CH.sub.2OH, OH, OR, SH, SR, C(O)N(R).sub.2, C(O)NHR, C(O)NH.sub.2, halide, tosylate, mesylate, SO.sub.2NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano, CF.sub.3, or Si(OR).sub.3; wherein R is independently selected from methyl, ethyl, isopropyl, n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or benzyl; M.sup.1 is selected from Li, Na, K, Rb, or Cs; and M.sup.2 is selected from Be, Mg, Ca, Sr, or Ba.

3. The lithium secondary battery of claim 1, wherein said redox pair with lithium is selected from the group consisting of lithium 4-methylbenzenesulfonate, lithium 3,5-dicarboxybenzenesulfonate, lithium 2,6-dimethylbenzene-1,4-disulfonate, 3,3′-((1,2-dithiane-4,5-diyl)bis(oxy))bis(N-hydroxypropanamide), 3,3′-((4-mercapto-1,2-phenylene)bis(oxy))bis(N-hydroxypropanamide), lithium aniline sulfonate, poly(lithium-4-styrenesulfonate, lithium sulfate, lithium phosphate, lithium phosphate monobasic, lithium trifluoromethanesulfonate, lithium 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate, lithium 2,6-di-tert-butylbenzene-1,4-disulfonate, lithium aniline sulfonate (wherein the sulfonate may be in any of para, meta and ortho positions), poly(lithium-4-styrenesulfonate, and combinations thereof.

4. The lithium secondary battery of claim 1, wherein said lithium ion-capturing group contains a salt that is dissociated into an anion and a cation in a liquid medium wherein said salt is selected from the group consisting of Li.sub.2CO.sub.3, Li.sub.2O, Li.sub.2C.sub.2O.sub.4, LiOH, LiX, ROCO.sub.2Li, HCOLi, ROLi, (ROCO.sub.2Li).sub.2, (CH.sub.2OCO.sub.2Li).sub.2, Li.sub.2S, Li.sub.xSO.sub.y, Na.sub.2CO.sub.3, Na.sub.2O, Na.sub.2C.sub.2O.sub.4, NaOH, NaX, ROCO.sub.2Na, HCONa, RONa, (ROCO.sub.2Na).sub.2, (CH.sub.2OCO.sub.2Na).sub.2, Na.sub.2S, Na.sub.xSO.sub.y, or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1, 1≤y≤4 and wherein said liquid medium to dissolve the salt contains a solvent selected from 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma-butyrolactone (y-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), a hydrofluoroether, hydrofluoro ether (FIFE), trifluoro propylene carbonate (FPC), methyl nonafluorobutyl ether (MFE), fluoroethylene carbonate (FEC), tris(trimethylsilyl)phosphite (TTSPi), triallyl phosphate (TAP), ethylene sulfate (DTD), 1,3-propane sultone (PS), propene sultone (PES), diethyl carbonate (DEC), alkylsiloxane (Si—O), alkyylsilane (Si—C), liquid oligomeric silaxane (—Si—O—Si—), tetraethylene glycol dimethylether (TEGDME), an ionic liquid solvent, and combinations thereof.

5. The lithium secondary battery of claim 1, wherein said lithium ion-capturing groups contain an ionic liquid having a cation selected from tetra-alkylammonium, di-, tri-, or tetra-alkylimidazolium, alkylpyridinium, dialkyl-pyrrolidinium, dialkylpiperidinium, tetraalkylphosphonium, trialkylsulfonium, or a combination thereof.

6. The lithium secondary battery of claim 1, wherein said lithium ion-capturing groups comprise an ionic liquid having an anion selected from the group consisting of BF.sub.4.sup.−, B(CN).sub.4.sup.−, CH.sub.3BF.sub.3.sup.−, CH.sub.2CHBF.sub.3.sup.−, CF.sub.3BF.sub.3.sup.−, C.sub.2F.sub.5BF.sub.3.sup.−, n-C.sub.3F.sub.7BF.sub.3.sup.−, n-C.sub.4F.sub.9BF.sub.3.sup.−, PF.sub.6.sup.−, CF.sub.3CO.sub.2.sup.−, CF.sub.3SO.sub.3.sup.−, N(SO.sub.2CF.sub.3).sub.2.sup.−, N(COCF.sub.3)(SO.sub.2CF.sub.3).sup.−, N(SO.sub.2F).sub.2.sup.−, N(CN).sub.2.sup.−, C(CN).sub.3.sup.−, SCN.sup.−, SeCN.sup.−, CuCl.sub.2.sup.−, AlCl.sub.4.sup.−, F(HF).sub.2.3.sup.−, and combinations thereof.

7. The lithium secondary battery of claim 1, wherein said lithium ion-capturing groups comprise an ionic liquid having a 1-ethyl-3-methylimidazolium (EMI) cation and an N,N-bis(trifluoromethane)sulfonamide (TFSI) anion.

8. The lithium secondary battery of claim 1, wherein said pores comprise mesoscaled pores having a pore size from 2 nm to 50 nm.

9. The lithium secondary battery of claim 1, wherein said electron-conducting porous structure has pore walls comprising an electron-conducting material selected from carbon nanotubes, carbon nanofibers, graphene sheets, expanded graphite platelets, carbon fibers, graphite fibers, graphite particles, needle coke, mesocarbon microbeads, carbon particles, carbon black, acetylene black, activated carbon particles, or a combination thereof.

10. The lithium secondary battery of claim 1, wherein said electron-conducting porous structure comprises a graphene foam.

11. The lithium secondary battery of claim 1, wherein said lithium ion-conducting polymer is selected from the group consisting of sulfonated polyaniline, sulfonated polypyrrole, a sulfonated polythiophene, sulfonated polyfuran, a sulfonated bi-cyclic polymer, and combinations thereof.

12. The lithium secondary battery of claim 1, wherein said lithium ion-conducting polymer is selected from the group consisting of sulfonated natural polyisoprene, sulfonated synthetic polyisoprene, sulfonated polybutadiene, sulfonated chloroprene rubber, sulfonated polychloroprene, sulfonated butyl rubber, sulfonated styrene-butadiene rubber, sulfonated nitrile rubber, sulfonated ethylene propylene rubber, sulfonated ethylene propylene diene rubber, metallocene-based sulfonated poly(ethylene-co-octene) elastomer, sulfonated poly(ethylene-co-butene) elastomer, sulfonated styrene-ethylene-butadiene-styrene elastomer, sulfonated epichlorohydrin rubber, sulfonated polyacrylic rubber, sulfonated silicone rubber, sulfonated fluorosilicone rubber, sulfonated perfluoroelastomers, sulfonated polyether block amides, sulfonated chlorosulfonated polyethylene, sulfonated ethylene-vinyl acetate, sulfonated thermoplastic elastomer, sulfonated protein resilin, sulfonated protein elastin, sulfonated ethylene oxide-epichlorohydrin copolymer, sulfonated polyurethane, sulfonated urethane-urea copolymer, and combinations thereof.

13. The lithium secondary battery of claim 1, wherein said lithium ion-conducting polymer is selected from the group consisting of poly(perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetra-fluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly (ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated poly chloro-trifluoroethylene, sulfonated perfluoroethylene-propylene copolymer, sulfonated ethylene-chlorotrifluoroethylene copolymer, sulfonated polyvinylidenefluoride, sulfonated copolymers of polyvinylidenefluoride with hexafluoropropene and tetrafluoroethylene, sulfonated copolymers of ethylene and tetrafluoroethylene, polybenzimidazole, and chemical derivatives, copolymers, and blends thereof.

14. The lithium secondary battery of claim 1, wherein said lithium ion-conducting polymer is selected from the group consisting of poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, and poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP) copolymer, modified polyacrylic acid-based copolymer, polyester polyamine amide-based copolymer, polycarboxylic acid-based copolymer, polyalkylol amino amide-based copolymer, polysiloxane polyacryl-based copolymer, polysiloxane polycarboxylic acid-based copolymer, polyalkoxylate-based copolymer, a copolymer of polyacryl and polyether, a derivative thereof, and combinations thereof.

15. The lithium secondary battery of claim 1, wherein said anode comprises an anode active material comprising an element selected from the group consisting of Si, Ge, Sn, Cd, Sb, Pb, Bi, Zn, Al, Co, Ni, Ti, or an alloy thereof, and combinations thereof.

16. The lithium secondary battery of claim 1, wherein said anode comprises an anode active material selected from the group consisting of: a) lithiated and un-lithiated silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); b) lithiated and un-lithiated alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; c) lithiated and un-lithiated oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, Mn, V, or Cd, and their mixtures, composites, or lithium-containing composites; d) lithiated and un-lithiated salts and hydroxides of Sn; e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; f) lithiated and un-lithiated particles of natural graphite, artificial graphite, mesocarbon microbeads, hard carbon (carbon materials that cannot be graphitized at a temperature higher than 2,500° C.), soft carbon (carbon materials that can be graphitized at a temperature higher than 2,500° C.), needle coke, polymeric carbon, carbon or graphite fiber segments, carbon nanofiber or graphitic nanofiber, carbon nanotube; and combinations thereof.

17. The lithium secondary battery of claim 1, wherein said anode comprises particles of an anode active material having a size from 10 nm to 1 μm.

18. The lithium secondary battery of claim 1, wherein said electrolyte is selected from the group consisting of a non-aqueous liquid electrolyte, polymer gel electrolyte, polymer electrolyte, quasi-solid electrolyte, solid-state inorganic electrolyte, ionic liquid electrolyte, and combinations thereof.

19. A lithium secondary battery comprising an anode, a cathode, a porous separator disposed between said anode and said cathode, an electrolyte, and a lithium ion reservoir disposed between said anode and said porous separator and configured to receive lithium ions from said cathode through said porous separator when said battery is charged and enable said lithium ions to enter said anode in a time-delayed manner, wherein said lithium ion reservoir comprises an electron-conducting or lithium ion-conducting porous framework structure having pores, having a pore size from 1 nm to 500 μm, and lithium-capturing groups residing in said pores, wherein said lithium-capturing groups are selected from (a) redox forming species that reversibly form a redox pair with a lithium ion when said battery is charged; (b) electron-donating groups interspaced between non-electron-donating groups; (c) anions and cations wherein the anions are more mobile than the cations; or (d) chemical reducing groups that partially reduce lithium ions from Li.sup.+1 to Li.sup.+δ, wherein 0<δ<1, wherein said electrolyte is a non-flammable quasi-solid electrolyte comprising a lithium salt dissolved in a liquid solvent having a lithium salt concentration from 3.5 M to 14.0 M so that the electrolyte exhibits a vapor pressure less than 0.01 kPa when measured at 20° C., a vapor pressure less than 60% of the vapor pressure of the liquid solvent alone, a flash point at least 20 degrees Celsius higher than a flash point of the liquid solvent alone, a flash point higher than 150° C., or no flash point.

20. A lithium secondary battery comprising an anode, a cathode, a porous separator disposed between said anode and said cathode, an electrolyte, and a lithium ion reservoir disposed between said anode and said porous separator and configured to receive lithium ions from said cathode through said porous separator when said battery is charged and enable said lithium ions to enter said anode in a time-delayed manner, wherein said lithium ion reservoir comprises an electron-conducting or lithium ion-conducting porous framework structure having pores, having a pore size from 1 nm to 500 μm, and lithium-capturing groups residing in said pores, wherein said lithium-capturing groups are selected from (a) redox forming species that reversibly form a redox pair with a lithium ion when said battery is charged; (b) electron-donating groups interspaced between non-electron-donating groups; (c) anions and cations wherein the anions are more mobile than the cations; or (d) chemical reducing groups that partially reduce lithium ions from Li.sup.+1 to Li.sup.+δ, wherein 0<δ<1, wherein said electrolyte is a non-flammable quasi-solid electrolyte comprising a lithium salt dissolved in a mixture of a liquid solvent and a liquid additive having a lithium salt concentration from 1.75 M to 5.0 M so that said electrolyte exhibits a vapor pressure less than 0.01 kPa when measured at 20° C., a vapor pressure less than 60% of the vapor pressure of said liquid solvent alone, a flash point at least 20 degrees Celsius higher than a flash point of said liquid solvent alone, a flash point higher than 150° C., or no flash point, wherein said liquid additive, different in composition than said liquid solvent, is selected from the group consisting of hydrofluoro ether (HFE), trifluoro propylene carbonate (FPC), methyl nonafluorobutyl ether (MFE), fluoroethylene carbonate (FEC), tris(trimethylsilyl)phosphite (TTSPi), triallyl phosphate (TAP), ethylene sulfate (DTD), 1,3-propane sultone (PS), propene sultone (PES), alkylsiloxane (Si—O), alkyylsilane (Si—C), liquid oligomeric silaxane (—Si—O—Si—), tetraethylene glycol dimethylether (TEGDME), canola oil, and combinations thereof and said liquid additive-to-said liquid solvent ratio in said mixture is from 5/95 to 95/5 by weight.

21. The lithium secondary battery of claim 1, wherein said electrolyte comprises a solvent selected from the group consisting of 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma-butyrolactone (γ-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), a hydrofluoroether, a room temperature ionic liquid solvent, and combinations thereof.

22. The lithium secondary battery of claim 1, wherein said electrolyte comprises a lithium salt selected from the group consisting of lithium perchlorate (LiClO.sub.4), lithium hexafluorophosphate (LiPF.sub.6), lithium borofluoride (LiBF.sub.4), lithium hexafluoroarsenide (LiAsF.sub.6, lithium trifluoro-metasulfonate (LiCF.sub.3SO.sub.3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF.sub.3SO.sub.2).sub.2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF.sub.2C.sub.2O.sub.4, lithium oxalyldifluoroborate (LiBF.sub.2C.sub.2O.sub.4), lithium nitrate (LiNO.sub.3, Li-fluoroalkyl-phosphates (LiPF.sub.3(CF.sub.2CF.sub.3).sub.3), lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, and combinations thereof.

23. The lithium secondary battery of claim 1, which is a lithium-ion battery, a rechargeable lithium metal battery, a lithium-sulfur battery, a lithium-selenium battery, or a lithium-air battery.

24. The lithium secondary battery of claim 1, wherein said porous separator comprises a film, woven fabric, or non-woven fabric formed using one or more selected from the group consisting of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ultrahigh-molecular weight polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, polycarbonate, polyimide, poly ether ether ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyethylene naphthalene, co-polymers thereof, blends thereof, and combinations thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1(A) Schematic of a rechargeable lithium metal battery containing a lithium metal anode and a lithium ion reservoir disposed between the anode and the porous separator;

(2) FIG. 1(B) Schematic of a lithium-ion battery containing an anode (comprising particles of an anode active material, such as Si and SnO.sub.2, an optional conductive additive, and an optional resin binder) and a lithium ion reservoir disposed between the anode and the porous separator.

(3) FIG. 2 Lithium ion conductivity values in a solid polymer mixture of a sulfonated polymer (S-PEEK or S-PTFE) and a conventional electrolyte polymer (PEO or PPO) plotted as a function of the sulfonated polymer proportion (each containing 30% by weight of lithium salt).

(4) FIG. 3 The actual charge storage capacity values of two cells each containing an anode of lithiated natural graphite particles and a cathode of GO/Li.sub.xV.sub.3O.sub.8 nanosheets are plotted as a function of the C rates. One cell contains a lithium ion reservoir disposed between the anode and the porous separator, but the other cell does not have such a reservoir.

(5) FIG. 4 The discharge capacity values of two Li—S cells (each featuring a Li foil as the anode active material and graphene-supported sulfur as the cathode active material) are plotted as a function of the number of charge/discharge cycles. One cell contains a lithium ion reservoir disposed between the Li metal anode and the separator, but the other cell does not have such a reservoir.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(6) The present invention provides a safe and high-performing rechargeable lithium battery, which can be any of the various types of lithium-ion cells (e.g. using graphite or Si as the main anode active material) or lithium metal cells (e.g. Li-metal oxide, Li—S, Li-air, and Li—Se cells, etc. using lithium metal as the main anode active material). For illustration purpose, the following discussion of preferred embodiments is primarily based on Li-ion cells and Li—S cells (as an example), but the same or similar principles and procedures are applicable to all other rechargeable lithium metal batteries (using lithium metal or metal alloy as the anode active material). The cathode active materials can be, for instance, a transition metal oxide (e.g. V.sub.2O.sub.5) or sulfide (e.g. MoS.sub.2), sulfur or polysulfide (e.g. lithium polysulfide), selenium, metal selenide, or just outside air (for a lithium-air cell).

(7) The present invention provides a lithium secondary battery, as schematically illustrated in FIG. 1(A) for a lithium metal battery (e.g. having a lithium metal foil or lithium alloy powder layer as the primary anode active material) or FIG. 1(B) for a lithium-ion battery (e.g. having a layer of particles of an anode active material, such as graphite, Si, Ge, Sn, SnO.sub.2, and optional conductive additive and resin binder). The lithium secondary battery comprises an anode, a cathode, a porous separator disposed between the anode and the cathode, an electrolyte, and a lithium ion reservoir disposed between the anode and the porous separator and configured to receive lithium ions from the cathode through the porous separator when the battery is charged and enable the lithium ions to enter the anode in a time-delayed manner. The lithium ion reservoir comprises an electron-conducting or lithium ion-conducting porous framework structure having pores, having a pore size from 1 nm to 500 μm, and lithium-capturing groups residing in the pores, wherein the lithium-capturing groups are selected from (a) redox forming species that reversibly form a redox pair with a lithium ion when the battery is charged; (b) electron-donating groups interspaced between non-electron-donating groups; (c) anions and cations wherein the anions are more mobile than the cations; or (d) chemical reducing groups that partially reduce lithium ions from Li.sup.+1 to Li.sup.+δ, wherein 0<δ<1.

(8) The term “in a time-delayed manner” means that (a) at least a portion (e.g. no less than 10%) of the lithium ions that enter the lithium ion reservoir does not immediately enter the anode layer (but being retained in the reservoir) when the battery is charged at a charging rate of 5 C or higher; or (b) when the external battery charger is switched off or unplugged, at least a portion of the of the lithium ions that enter the lithium ion reservoir remains in the reservoir and continues to enter the anode and the anode active material (i.e. the internal charging procedure continues even though the external charger is off). The presently invented lithium ion reservoir strategy enables the charging process to be conducted in a time-delayed manner to allow most of the available lithium ions to eventually get charged into the anode active material. Without such a lithium ion reservoir, fast charging can lead to either a significantly lower amount of lithium ions that actually get intercalated or inserted into the anode active material or the formation of lithium metal plating and dangerous lithium dendrite formation.

(9) In some embodiments, the lithium-capturing group is selected from a molecule having a core or backbone structure and at least a side group that is ionic or electron-rich in nature. The core or backbone structure may contain an aryl, heterocycloalkyl, crown etheryl, cyclamyl, cyclenyl, 1,4,7-triazacyclononayl, hexacyclenyl, cryptandyl, naphtalenyl, antracenyl, phenantrenyl, tetracenyl, chrysenyl, tryphenylenyl, pyrenyl, pentacenyl, single-benzene or cyclic structure, double-benzene or bi-cyclic structure, or multiple-cyclic structure having 3-10 benzene rings. The side group may contain CO.sub.2H, CO.sub.2M.sup.1, CO.sub.2R, SO.sub.3H, SO.sub.3M.sup.1, PO.sub.3H.sub.2, PO.sub.3M.sup.1.sub.2, PO.sub.3M.sup.1H, PO.sub.4H.sub.2, PO.sub.4M.sup.1.sub.2, PO.sub.4M.sup.1H, PO.sub.4M.sup.2, C(O)NHOH, NH.sub.2, NHR, N(R).sub.2, NO.sub.2, COOR, CHO, CH.sub.2OH, OH, OR, SH, SR, C(O)N(R).sub.2, C(O)NHR, C(O)NH.sub.2, halide, tosylate, mesylate, SO.sub.2NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano, CF.sub.3, or Si(OR).sub.3; wherein R is independently selected from methyl, ethyl, isopropyl, n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or benzyl; M.sup.1 is selected from Li, Na, K, Rb, or Cs; M.sup.2 is selected from Be, Mg, Ca, Sr, or Ba.

(10) In some specific embodiments, the redox pair with lithium is selected from lithium 4-methylbenzenesulfonate, lithium 3,5-dicarboxybenzenesulfonate, lithium 2,6-dimethylbenzene-1,4-disulfonate, 3,3′-((1,2-dithiane-4,5-diyl)bis(oxy))bis(N-hydroxypropanamide), 3,3′-((4-mercapto-1,2-phenylene)bis(oxy))bis(N-hydroxypropanamide), lithium aniline sulfonate, poly(lithium-4-styrenesulfonate, lithium sulfate, lithium phosphate, lithium phosphate monobasic, lithium trifluoromethanesulfonate, lithium 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate, lithium 2,6-di-tert-butylbenzene-1,4-disulfonate, lithium aniline sulfonate (wherein the sulfonate may be in any of para, meta and ortho positions), poly(lithium-4-styrenesulfonate, or a combination thereof.

(11) Electron-donating groups may be selected from those molecules having one to 10 benzene rings or cyclic structure as the core/backbone portion having conjugated double bonds, acidic groups, etc. Examples include sodium 4-methylbenzenesulfonate, sodium 3,5-dicarboxybenzenesulfonate, sodium 2,6-dimethylbenzene-1,4-disulfonate, and sodium aniline sulfonate. These molecules in the lithium ion reservoir appear to be capable of partially reducing the incoming lithium ions that pass through the porous separator from the cathode.

(12) The lithium ion-capturing group may contain a salt that is dissociated into an anion and a cation in a liquid medium (typically an organic solvent). Non-limiting examples of these salts are Li.sub.2CO.sub.3, Li.sub.2O, Li.sub.2C.sub.2O.sub.4, LiOH, LiX, ROCO.sub.2Li, HCOLi, ROLi, (ROCO.sub.2Li).sub.2, (CH.sub.2OCO.sub.2Li).sub.2, Li.sub.2S, Li.sub.xSO.sub.y, Na.sub.2CO.sub.3, Na.sub.2O, Na.sub.2C.sub.2O.sub.4, NaOH, NaX, ROCO.sub.2Na, HCONa, RONa, (ROCO.sub.2Na).sub.2, (CH.sub.2OCO.sub.2Na).sub.2, Na.sub.2S, Na.sub.xSO.sub.y, or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1, 1≤y≤4. The liquid medium to dissolve these salts may contain a solvent selected from 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma-butyrolactone (γ-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), a hydrofluoroether, hydrofluoro ether (HFE), trifluoro propylene carbonate (FPC), methyl nonafluorobutyl ether (MFE), fluoroethylene carbonate (FEC), tris(trimethylsilyl)phosphite (TTSPi), triallyl phosphate (TAP), ethylene sulfate (DTD), 1,3-propane sultone (PS), propene sultone (PES), diethyl carbonate (DEC), alkylsiloxane (Si—O), alkyylsilane (Si—C), liquid oligomeric silaxane (—Si—O—Si—), tetraethylene glycol dimethylether (TEGDME), an ionic liquid solvent, or a combination thereof.

(13) The lithium ion-capturing groups may contain ionic liquids, which are low melting temperature salts that are in a molten or liquid state when above a desired temperature. For instance, a salt is considered as an ionic liquid if its melting point is below 100° C. If the melting temperature is equal to or lower than room temperature (25° C.), the salt is referred to as a room temperature ionic liquid (RTIL). The desired ionic liquids for use in the presently invented lithium ion reservoir preferably have a melting point lower than 60° C., more preferably lower than 0° C., and further more preferably lower than −20° C. The IL salts are characterized by weak interactions, due to the combination of a large cation and a charge-delocalized anion. This results in a low tendency to crystallize due to flexibility (anion) and asymmetry (cation). The anions of the ionic liquid may be selected to be more mobile than the cations.

(14) A typical and well-known ionic liquid is formed by the combination of a 1-ethyl-3-methylimidazolium (EMI) cation and an N,N-bis(trifluoromethane)sulfonamide (TFSI) anion. This combination gives a fluid with an ionic conductivity comparable to many organic electrolyte solutions and a low decomposition propensity and low vapor pressure up to ˜300-400° C. This implies a generally low volatility and non-flammability and, hence, a much safer electrolyte for batteries.

(15) Ionic liquids are basically composed of organic ions that come in an essentially unlimited number of structural variations owing to the preparation ease of a large variety of their components. Thus, various kinds of salts can be used to design the ionic liquid that has the desired properties for a given application. These include, among others, imidazolium, pyrrolidinium and quaternary ammonium salts as cations and bis(trifluoromethanesulfonyl) imide, bis(fluorosulfonyl)imide, and hexafluorophosphate as anions. Based on their compositions, ionic liquids come in different classes that basically include aprotic, protic and zwitterionic types, each one suitable for a specific application.

(16) Common cations of room temperature ionic liquids (RTILs) include, but not limited to, tetraalkylammonium, di-, tri-, and tetra-alkylimidazolium, alkylpyridinium, dialkyl-pyrrolidinium, dialkylpiperidinium, tetraalkylphosphonium, and trialkylsulfonium. Common anions of RTILs include, but not limited to, BF.sub.4.sup.−, B(CN).sub.4.sup.−, CH.sub.3BF.sub.3.sup.−, CH.sub.2CHBF.sub.3.sup.−, CF.sub.3BF.sub.3.sup.−, C.sub.2F.sub.5BF.sub.3.sup.−, n-C.sub.3F.sub.7BF.sub.3.sup.−, n-C.sub.4F.sub.9BF.sub.3.sup.−, PF.sub.6.sup.−, CF.sub.3CO.sub.2.sup.−, CF.sub.3SO.sub.3.sup.−, N(SO.sub.2CF.sub.3).sub.2.sup.−, N(COCF.sub.3)(SO.sub.2CF.sub.3).sup.−, N(SO.sub.2F).sub.2.sup.−, N(CN).sub.2.sup.−, C(CN).sub.3.sup.−, SCN.sup.−, SeCN.sup.−, CuCl.sub.2.sup.−, AlCl.sub.4.sup.−, F(HF).sub.2.3.sup.−, etc. Relatively speaking, the combination of imidazolium- or sulfonium-based cations and complex halide anions such as AlCl.sub.4.sup.−, BF.sub.4.sup.−, CF.sub.3CO.sub.2.sup.−, CF.sub.3SO.sub.3.sup.−, NTf.sub.2.sup.−, N(SO.sub.2F).sub.2.sup.−, or F(HF).sub.2.3.sup.− results in RTILs with good working conductivities.

(17) In the lithium secondary battery, the pores preferably contain mesoscaled pores having a pore size from 2 nm to 100 nm, preferably from 2 nm to 50 nm. These mesopores are particularly effective in holding the lithium-capturing groups inside the pores to perform their intended functions.

(18) In some embodiments, the electron-conducting porous structure has pore walls comprising an electron-conducting material selected from carbon nanotubes, carbon nanofibers, graphene sheets, expanded graphite platelets, carbon fibers, graphite fibers, graphite particles, needle coke, mesocarbon microbeads, carbon particles, carbon black, acetylene black, activated carbon particles, or a combination thereof. In some embodiments, the electron-conducting material is made into a fabric (woven or non-woven), paper, or foam structure. The foam structure may be a closed-cell foam, but preferably an open-cell foam. The construction or production of these electron-conducting materials in a fabric, paper, or foam structure is well-known in the art.

(19) Preferably, the electron-conducting porous structure contains a graphene foam. Generally speaking, a foam (or foamed material) is composed of pores (or cells) and pore walls (the solid portion of a foam material). The pores can be interconnected to form an open-cell foam. A graphene foam is composed of pores and pore walls that contain a graphene material. There are several major methods of producing graphene foams:

(20) The first method is the hydrothermal reduction of graphene oxide hydrogel that typically involves sealing graphene oxide (GO) aqueous suspension in a high-pressure autoclave and heating the GO suspension under a high pressure (tens or hundreds of atm) at a temperature typically in the range from 180−300° C. for an extended period of time (typically 12-36 hours). A useful reference for this method is given here: Y. Xu, et al. “Self-Assembled Graphene Hydrogel via a One-Step Hydrothermal Process,” ACS Nano 2010, 4, 4324-4330.

(21) The second method is based on a template-assisted catalytic CVD process, which involves CVD deposition of graphene on a sacrificial template (e.g. Ni foam). The graphene material conforms to the shape and dimensions of the Ni foam structure. The Ni foam is then etched away using an etching agent, leaving behind a monolith of graphene skeleton that is essentially an open-cell foam. A useful reference for this method is given here: Zongping Chen, et al., “Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition,” Nature Materials, 10 (June 2011) 424-428. There are several problems associated with such a process: (a) the catalytic CVD is intrinsically a very slow, highly energy-intensive, and expensive process; (b) the etching agent is typically a highly undesirable chemical and the resulting Ni-containing etching solution is a source of pollution. It is very difficult and expensive to recover or recycle the dissolved Ni metal from the etchant solution. (c) It is challenging to maintain the shape and dimensions of the graphene foam without damaging the cell walls when the Ni foam is being etched away. The resulting graphene foam is typically very brittle and fragile.

(22) The third method of producing graphene foam also makes use of a sacrificial material (e.g. colloidal polystyrene particles, PS) that is coated with graphene oxide sheets using a self-assembly approach. For instance, Choi, et al. prepared chemically modified graphene (CMG) paper in two steps: fabrication of free-standing PS/CMG films by vacuum filtration of a mixed aqueous colloidal suspension of CMG and PS (2.0 m PS spheres), followed by removal of PS beads to generate 3D macro-pores. [B. G. Choi, et al., “3D Macroporous Graphene Frameworks for Supercapacitors with High Energy and Power Densities,” ACS Nano, 6 (2012) 4020-4028.] Choi, et al. fabricated well-ordered free-standing PS/CMG paper by filtration, which began with separately preparing a negatively charged CMG colloidal and a positively charged PS suspension. A mixture of CMG colloidal and PS suspension was dispersed in solution under controlled pH (=2), where the two compounds had the same surface charges (zeta potential values of +13±2.4 mV for CMG and +68±5.6 mV for PS). When the pH was raised to 6, CMGs (zeta potential=−29±3.7 mV) and PS spheres (zeta potential=+51±2.5 mV) were assembled due to the electrostatic interactions and hydrophobic characteristics between them, and these were subsequently integrated into PS/CMG composite paper through a filtering process.

(23) The fourth method of producing a graphene foam (Aruna Zhamu and Bor Z. Jang, “Highly Conductive Graphene Foams and Process for Producing Same,” U.S. patent application Ser. No. 14/120,959 (Jul. 17, 2014); U.S. Publication No. 20160019995 (Jan. 21, 2016)) comprises:

(24) (a) preparing a graphene dispersion having particles of an anode active material and a graphene material dispersed in a liquid medium, wherein the graphene material is selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, chemically functionalized graphene, or a combination thereof and wherein the dispersion contains an optional blowing agent;
(b) dispensing and depositing the graphene dispersion onto a surface of a supporting substrate (e.g. plastic film, rubber sheet, metal foil, glass sheet, paper sheet, etc.) to form a wet layer of graphene-anode material mixture, wherein the dispensing and depositing procedure includes subjecting the graphene dispersion to an orientation-inducing stress;
(c) partially or completely removing the liquid medium from the wet layer of graphene-anode material mixture to form a dried layer of material mixture having a content of non-carbon elements (e.g. O, H, N, B, F, Cl, Br, I, etc.) no less than 5% by weight; and
(d) heat treating the dried layer of material mixture at a first heat treatment temperature from 100° C. to 3,200° C. at a desired heating rate sufficient to induce volatile gas molecules from the non-carbon elements or to activate the blowing agent for producing the anode layer.

(25) The solid graphene foam in the anode layer typically has a density from 0.01 to 1.7 g/cm.sup.3 (more typically from 0.1 to 1.5 g/cm.sup.3, and even more typically from 0.1 to 1.0 g/cm.sup.3, and most typically from 0.2 to 0.75 g/cm.sup.3), or a specific surface area from 50 to 3,000 m.sup.2/g (more typically from 200 to 2,000 m.sup.2/g, and most typically from 500 to 1,500 m.sup.2/g).

(26) This optional blowing agent is not required if the graphene material has a content of non-carbon elements (e.g. O, H, N, B, F, Cl, Br, I, etc.) no less than 5% by weight (preferably no less than 10%, further preferably no less than 20%, even more preferably no less than 30% or 40%, and most preferably up to 50%). The subsequent high temperature treatment serves to remove a majority of these non-carbon elements from the graphene material, generating volatile gas species that produce pores or cells in the solid graphene material structure. In other words, quite surprisingly, these non-carbon elements play the role of a blowing agent. Hence, an externally added blowing agent is optional (not required). However, the use of a blowing agent can provide added flexibility in regulating or adjusting the porosity level and pore sizes for a desired application. The blowing agent is typically required if the non-carbon element content is less than 5%, such as pristine graphene that is essentially all-carbon.

(27) In certain embodiments, the lithium ion-conducting porous structure comprises a polymer foam or polymer fabric having pores and pore walls. The pore walls comprise a lithium ion-conducting polymer having a lithium ion conductivity from 10.sup.−8 to 10.sup.−2 S/cm when measured at 25° C.

(28) In some embodiments, the lithium ion-conducting polymer is selected from sulfonated polyaniline, sulfonated polypyrrole, a sulfonated polythiophene, sulfonated polyfuran, a sulfonated bi-cyclic polymer, or a combination thereof. These sulfonated polymers are found to be both electron-conducting and lithium ion-conducting.

(29) In some embodiments, the lithium ion-conducting polymer contains a sulfonated rubber or elastomer selected from sulfonated natural polyisoprene, sulfonated synthetic polyisoprene, sulfonated polybutadiene, sulfonated chloroprene rubber, sulfonated polychloroprene, sulfonated butyl rubber, sulfonated styrene-butadiene rubber, sulfonated nitrile rubber, sulfonated ethylene propylene rubber, sulfonated ethylene propylene diene rubber, metallocene-based sulfonated poly(ethylene-co-octene) elastomer, sulfonated poly(ethylene-co-butene) elastomer, sulfonated styrene-ethylene-butadiene-styrene elastomer, sulfonated epichlorohydrin rubber, sulfonated polyacrylic rubber, sulfonated silicone rubber, sulfonated fluorosilicone rubber, sulfonated perfluoroelastomers, sulfonated polyether block amides, sulfonated chlorosulfonated polyethylene, sulfonated ethylene-vinyl acetate, sulfonated thermoplastic elastomer, sulfonated protein resilin, sulfonated protein elastin, sulfonated ethylene oxide-epichlorohydrin copolymer, sulfonated polyurethane, sulfonated urethane-urea copolymer, or a combination thereof.

(30) In some embodiments, the lithium ion-conducting polymer is selected from the group consisting of poly(perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetra-fluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly (ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated poly chloro-trifluoroethylene, sulfonated perfluoroethylene-propylene copolymer, sulfonated ethylene-chlorotrifluoroethylene copolymer, sulfonated polyvinylidenefluoride, sulfonated copolymers of polyvinylidenefluoride with hexafluoropropene and tetrafluoroethylene, sulfonated copolymers of ethylene and tetrafluoroethylene, polybenzimidazole, and chemical derivatives, copolymers, and blends thereof.

(31) The production of sulfonation polymers is well-known in the art. One may produce a sulfonated polymer by polymerizing a sulfonated monomer or a monomer containing a sulfonyl group (e.g. T. G. Dang, et al. U.S. Publication No. 2005/0165213 (Jul. 28, 2005)). Preferably, one may sulfonate a polymer by immersing the polymer in a concentrated sulfuric acid (e.g. concentration >90%). For details one may consult C. J. Cornelius, et al. U.S. Pat. No. 7,301,002 (Nov. 27, 2007) and references cited therein. In some embodiments, a desired polymer is made into fibers and then a fabric or paper structure, which is followed by a sulfonation treatment. Alternatively, one may use a chemical blowing agent or physical blowing agent to assist in forming a polymer foam structure (e.g. a film or sheet shape). The resulting porous structure (fabric, paper, or foam, etc.) may then be soaked with the lithium ion-capturing molecules or ionic salt solution discussed above.

(32) In some embodiments, the lithium ion-conducting polymer is selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, and poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP) copolymer, modified polyacrylic acid-based copolymer, polyester polyamine amide-based copolymer, polycarboxylic acid-based copolymer, polyalkylol amino amide-based copolymer, polysiloxane polyacryl-based copolymer, polysiloxane polycarboxylic acid-based copolymer, polyalkoxylate-based copolymer, a copolymer of polyacryl and polyether, a derivative thereof, or a combination thereof. These materials can be readily made into a porous structure such as a fabric, paper, or foam structure.

(33) There are several approaches that can be followed to form a lithium ion reservoir composed of a conducting framework porous structure (foam, paper, fabric, etc.) having pores filled with lithium ion-capturing molecules or ions. It may be noted that these molecules or ions either have a low melting point (lower than 100° C. or even <25° C.) and, thus, can be easily melted to become a highly flowable state, or can be dissolved in a liquid solvent to become solution. Hence, these lithium ion-capturing species can be readily made to permeate into pores of the porous framework structure. Such permeation can be accomplished by using, for instance, the following procedures: (a) Solution permeation: This includes dispersion or dissolution of molecules or ions in water or a solvent to form a solution or suspension, followed by coating or spraying the solution onto the porous structure or by dipping the porous structure into this solution or suspension; or (b) Melt mixing: This includes bringing the molecules or ionic species into a molten (liquid) state and allowing the liquid to permeate into the pores of the porous structure using, coating, spraying, dipping, etc.

(34) Specifically, one may dispense and deposit a layer of the species in a liquid or solution state onto a primary surface of the porous structure using air pressure-assisted spraying, ultrasonic spraying, casting, coating, and the like, preferably followed by a roll-pressing or other means of consolidating the lithium ion reservoir layer.

(35) In the lithium-ion battery, the anode (sometimes referred to as anode electrode) typically is composed of an anode active material, a conductive additive (e.g. carbon black, acetylene black, graphite platelets, carbon nanotubes, etc.), and a resin binder (e.g. the well-known SBR rubber, PVDF, CMC, etc.). In some embodiments, the anode electrode may comprise an anode active material comprising an element selected from Si, Ge, Sn, Cd, Sb, Pb, Bi, Zn, Al, Co, Ni, Ti, or an alloy thereof.

(36) In some embodiments, the anode comprises an anode active material selected from the group consisting of: (A) lithiated and un-lithiated silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (B) lithiated and un-lithiated alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (C) lithiated and un-lithiated oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, Mn, V, or Cd, and their mixtures, composites, or lithium-containing composites; (D) lithiated and un-lithiated salts and hydroxides of Sn; (E) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; (F) lithiated and un-lithiated particles of natural graphite, artificial graphite, mesocarbon microbeads, hard carbon (commonly defined as the carbon materials that cannot be graphitized at a temperature higher than 2,500° C.), soft carbon (carbon materials that can be graphitized at a temperature higher than 2,500° C.), needle coke, polymeric carbon, carbon or graphite fiber segments, carbon nanofiber or graphitic nanofiber, carbon nanotube; and combinations thereof.

(37) The anode of a lithium-ion battery may be made by using the well-known slurry coating method. For instance, one may mix particles of an anode active material (e.g. carbon-coated Si nanoparticles or nanowires), a resin binder (e.g. SBR rubber, CMC, polyacrylamide), and a conductive filler (e.g. particles of acetylene black, carbon black, or carbon nanotubes) in water or an organic solvent (e.g. NMP) to form a slurry. The slurry is then coated on one primary surface or both primary surfaces of a Cu foil and then dried to form an anode electrode. For the anode of a lithium metal battery, one may simply use a thin Li foil attached to a Cu foil or a graphene-based current collector.

(38) The particles of an anode active material (e.g. Si, Ge, SiO.sub.x, Sn, SnO.sub.2, etc., wherein x=0.01-1.9) preferably have a diameter from 5 nm to 1 μm, more preferably from 10 to 500 nm, and most preferably from 20 to 100 nm.

(39) There is no restriction on the type of porous separator that can be used in the presently invented lithium battery. A porous separator (e.g. polyolefin-based, non-woven of electrically insulating fibers, etc.) may be used in lithium secondary batteries for the purpose of preventing short circuiting between an anode and a cathode, but having pores serving as a passage for lithium ions. Most of the commercially available lithium batteries make use of a polyolefin (e.g. polyethylene, polypropylene, PE/PP copolymer, etc.) as a separator.

(40) There is essentially no restriction on the type of cathode active materials for use in the presently invented protected lithium cells. The cathode active material in the cathode in this rechargeable alkali metal battery may be selected from sulfur, selenium, tellurium, lithium sulfide, lithium selenide, lithium telluride, sodium sulfide, sodium selenide, sodium telluride, a chemically treated carbon or graphite material having an expanded inter-graphene spacing d.sub.002 of at least 0.4 nm, or an oxide, dichalcogenide, trichalcogenide, sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, nickel, or a combination thereof. Preferred cathode active materials include non-lithiated and slightly lithiated compounds having relatively high lithium or sodium storage capacities, such as TiS.sub.2, MoS.sub.2, MnO.sub.2, COO.sub.2, and V.sub.2O.sub.5.

(41) A novel family of 2D metal carbides or metal carbonides, now commonly referred to as MXenes, can be used as a cathode active material. MXenes can be produced by partially etching out certain elements from layered structures of metal carbides such as Ti.sub.3AlC.sub.2. For instance, an aqueous 1 M NH.sub.4HF.sub.2 was used at room temperature as the etchant for Ti.sub.3AlC.sub.2. Typically, MXene surfaces are terminated by O, OH, and/or F groups, which is why they are usually referred to as M.sub.n+1X.sub.nT.sub.x, where M is an early transition metal, X is C and/or N, T represents terminating groups (O, OH, and/or F), n=1, 2, or 3, and x is the number of terminating groups. The MXene materials investigated include Ti.sub.2CT.sub.x, (Ti.sub.0.5, Nb.sub.0.5).sub.2CT.sub.x, Nb.sub.2CT.sub.x, V.sub.2CT.sub.x, Ti.sub.3C.sub.2T.sub.x, (V.sub.0.5, Cr.sub.0.5).sub.3C.sub.2T.sub.x, Ti.sub.3CNT.sub.x, Ta.sub.4C.sub.3T.sub.x, and Nb.sub.4C.sub.3T.sub.x.

(42) In an embodiment, the cathode layer contains an air cathode and the battery is a lithium-air battery. In another embodiment, the cathode active material is selected from sulfur or lithium polysulfide and the battery is a lithium-sulfur battery. In yet another embodiment, the cathode active material may be selected from an organic or polymeric material capable of capturing or storing lithium ions (e.g. via reversibly forming a redox pair with lithium ion).

(43) In the cathode electrode of a lithium-ion battery, the cathode active material may be selected from a metal oxide/phosphate/sulfide/halogenide, an inorganic material, an organic or polymeric material, or a combination thereof: a) the group of metal oxide, metal phosphate, and metal sulfides consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium transition metal oxide, lithium-mixed metal oxide (e.g. the well-known NCM, NCA, etc.), transition metal fluoride, transition metal chloride, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphates, transition metal sulfides, and combinations thereof. a. In particular, the lithium vanadium oxide may be selected from the group consisting of VO.sub.2, Li.sub.xVO.sub.2, V.sub.2O.sub.5, Li.sub.xV.sub.2O.sub.5, V.sub.3O.sub.8, Li.sub.xV.sub.3O.sub.8, LixV.sub.3O.sub.7, V.sub.4O.sub.9, LixV.sub.4O.sub.9, V.sub.6O.sub.13, LixV.sub.6O.sub.13, their doped versions, their derivatives, and combinations thereof, wherein 0.1<x<5; b. Lithium transition metal oxide may be selected from a layered compound LiMO.sub.2, spinel compound LiM.sub.2O.sub.4, olivine compound LiMPO.sub.4, silicate compound Li.sub.2MSiO.sub.4, tavorite compound LiMPO.sub.4F, borate compound LiMBO.sub.3, or a combination thereof, wherein M is a transition metal or a mixture of multiple transition metals. b) an inorganic material selected from: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (d) boron nitride, or (e) sulfur, sulfur compound, lithium polysulfide (f) a combination thereof. In particular, TiS.sub.2, TaS.sub.2, MoS.sub.2, NbSe.sub.3, non-lithiated MnO.sub.2, COO.sub.2, iron oxide, vanadium oxide, or a combination thereof may be used as a cathode active material in a lithium metal cell. c) the organic material or polymeric material may be selected from poly(anthraquinonyl sulfide) (PAQS), a lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), poly(anthraquinonyl sulfide), pyrene-4,5,9,10-tetraone (PYT), polymer-bound PYT, quino(triazene), redox-active organic material, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dyhydroxy anthraquinone) (PADAQ), phosphazene disulfide polymer ([(NPS.sub.2).sub.3]n), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, hexaazatrinaphtylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT(CN).sub.6), 5-benzylidene hydantoin, isatine lithium salt, pyromellitic diimide lithium salt, tetrahydroxy-p-benzoquinone derivatives (THQLi.sub.4), N,N′-diphenyl-2,3,5,6-tetraketopiperazine (PHP), N,N′-diallyl-2,3,5,6-tetraketopiperazine (AP), N,N′-dipropyl-2,3,5,6-tetraketopiperazine (PRP), a thioether polymer, a quinone compound, 1,4-benzoquinone, 5,7,12,14-pentacenetetrone (PT), 5-amino-2,3-dihydro-1,4-dyhydroxy anthraquinone (ADDAQ), 5-amino-1,4-dyhydroxy anthraquinone (ADAQ), calixquinone, Li.sub.4C.sub.6O.sub.6, Li.sub.2C.sub.6O.sub.6, Li.sub.6C.sub.6O.sub.6, or a combination thereof.

(44) The thioether polymer is selected from poly[methanetetryl-tetra(thiomethylene)](PMTTM), poly(2,4-dithiopentanylene) (PDTP), a polymer containing poly(ethene-1,1,2,2-tetrathiol) (PETT) as a main-chain thioether polymers, a side-chain thioether polymer having a main-chain consisting of conjugating aromatic moieties, and having a thioether side chain as a pendant, poly(2-phenyl-1,3-dithiolane) (PPDT), poly(1,4-di(1,3-dithiolan-2-yl)benzene) (PDDTB), poly(tetrahydrobenzodithiophene) (PTHBDT), poly[1,2,4,5-tetrakis(propylthio)benzene] (PTKPTB, or poly[3,4(ethylenedithio)thiophene] (PEDTT).

(45) The organic material may include a phthalocyanine compound selected from copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium phthalocyanine, magnesium phthalocyanine, manganous phthalocyanine, dilithium phthalocyanine, aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, a metal-free phthalocyanine, a chemical derivative thereof, or a combination thereof.

(46) The cathode of a lithium-ion battery may be made by using the well-known slurry coating method. For instance, one may mix particles of a cathode active material (e.g. particles of NMC, NCA, LiCoO.sub.2, TiS.sub.2, graphene-protected S particles, etc.), a resin binder (e.g. PVDF), and a conductive filler (e.g. particles of acetylene black, carbon black, or carbon nanotubes) in an organic solvent (e.g. NMP) to form a slurry. The slurry is then coated on one primary surface or both primary surfaces of an Al foil and then dried to form a cathode electrode.

(47) The electrolytes that can be used in the lithium battery may be selected from any lithium metal salt that is dissolvable in a solvent to produce an electrolyte. Preferably, the metal salt is selected from lithium perchlorate (LiClO.sub.4), lithium hexafluorophosphate (LiPF.sub.6), lithium borofluoride (LiBF.sub.4), lithium hexafluoroarsenide (LiAsF.sub.6), lithium trifluoro-metasulfonate (LiCF.sub.3SO.sub.3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF.sub.3SO.sub.2).sub.2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF.sub.2C.sub.2O.sub.4), lithium oxalyldifluoroborate (LiBF.sub.2C.sub.2O.sub.4), lithium nitrate (LiNO.sub.3), li-fluoroalkyl-phosphates (LiPF.sub.3(CF.sub.2CF.sub.3).sub.3), lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), or a combination thereof.

(48) The electrolytes used may contain a solvent selected from 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma-butyrolactone (γ-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), a hydrofluoroether, a room temperature ionic liquid solvent, or a combination thereof. The ionic liquid may also be used as an electrolyte for the lithium battery.

(49) The anode of a lithium-ion battery may contain anode active material particles selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo.sub.2O.sub.4; (f) particles of graphite and carbon; and (g) combinations thereof.

(50) At the anode side, the anode active material of a lithium metal battery may contain a layer of Li metal or alloy (>70% by weight of Li, preferably >80%, and more preferably >90%). Alternatively, the Li metal or alloy may be supported by a nanostructure composed of conductive nanofilaments. For instance, multiple conductive nanofilaments are processed to form an integrated aggregate structure, preferably in the form of a closely packed web, mat, or paper, characterized in that these filaments are intersected, overlapped, or somehow bonded (e.g., using a binder material) to one another to form a network of electron-conducting paths. The integrated structure has substantially interconnected pores to accommodate electrolyte. The nanofilament may be selected from, as examples, a carbon nanofiber (CNF), graphite nanofiber (GNF), carbon nanotube (CNT), metal nanowire (MNW), conductive nanofibers obtained by electrospinning, conductive electrospun composite nanofibers, nanoscaled graphene platelet (NGP), or a combination thereof. The nanofilaments may be bonded by a binder material selected from a polymer, coal tar pitch, petroleum pitch, mesophase pitch, coke, or a derivative thereof.

(51) Nanofibers may be selected from the group consisting of an electrically conductive electrospun polymer fiber, electrospun polymer nanocomposite fiber comprising a conductive filler, nanocarbon fiber obtained from carbonization of an electrospun polymer fiber, electrospun pitch fiber, and combinations thereof. For instance, a nanostructured electrode can be obtained by electrospinning of polyacrylonitrile (PAN) into polymer nanofibers, followed by carbonization of PAN. It may be noted that some of the pores in the structure, as carbonized, are greater than 100 nm and some smaller than 100 nm.

(52) In summary, a possible lithium cell may be comprised of an alkali metal layer (e.g. Li foil, etc.) or an anode active material particle layer (e.g. particles of Si plus conductive additive and binder resin), an anode current collector (e.g. Cu foil and/or a nanostructure of interconnected conductive filaments) supporting the anode layer, a lithium ion reservoir layer, a porous separator and an electrolyte phase, a cathode, and an optional cathode current collector (e.g. Al foil and/or or a nanostructure of interconnected conductive filaments, such as graphene sheets and carbon nanofibers) to support the cathode layer. These layers may be laminated together to form a battery cell, followed by injection of a liquid electrolyte (if electrolyte is not yet incorporated in the laminate). The battery cell production procedures are well-known in battery industry.

(53) The following examples serve to illustrate the preferred embodiments of the present invention and should not be construed as limiting the scope of the invention:

Example 1: Synthesis of Sulfonated Polyaniline (S-PANi)

(54) The chemical synthesis of the S-PANi polymers was accomplished by reacting polyaniline with concentrated sulfuric acid. The procedure was similar to that used by Epstein, et al. (U.S. Pat. No. 5,109,070, Apr. 28, 1992). The resulting S-PANi can be represented by the following Formula 1, with R.sub.1, R.sub.2, R.sub.3, and R.sub.4 group being H, SO.sub.3 or SO.sub.3H (R.sub.5=H) with the content of the latter two being varied between 30% and 75% (i.e., the degree of sulfonation varied between 30% and 75%).

(55) ##STR00001##

(56) The lithium ion conductivity of these SO.sub.3.sup.− or SO.sub.3H-based S-PANi compositions was in the range from 8.5×10.sup.−5 S/cm to 4.6×10.sup.−3 S/cm and their electron conductivity in the range from 0.1 S/cm to 0.5 S/cm when the degree of sulfonation was from approximately 30% to 75% (with y being approximately 0.4-0.6).

(57) The porous framework for the lithium ion reservoir layer was obtained by dissolving S-PANi in water to form a polymer-water solution, which was freeze-dried to obtain a sponge-like foamed structure. A porosity level from approximately 20% to 85% was achieved. Upon fully drying the foam, the pores in several foam structures were impregnated with several different lithium ion-capturing species, respectively: including lithium 4-methylbenzenesulfonate, lithium aniline sulfonate, lithium sulfate, lithium phosphate, and an ionic liquid having a 1-ethyl-3-methylimidazolium (EMI) cation and an N,N-bis(trifluoromethane)sulfonamide (TFSI) anion.

(58) The resulting lithium ion-capturing reservoir layers were then implemented in several lithium cells, including lithium-ion cells (“graphite anode+NCA cathode” and “anode of graphene-protected Si particles+NCM cathode”) and lithium metal cells (“Li metal foil anode+MoS.sub.2 cathode” and “Li metal anode+graphene/S cathode).

(59) We have observed that, by implementing a lithium ion reservoir between the anode layer and the porous separator layer, one enables the resulting lithium-ion batteries or lithium metal batteries to be fast-charged at a rate of 10 C to 30 C with only a 10% capacity reduction as compared to the battery measured at a rate of 0.5 C. In contrast, when recharged at a high C rate (e.g. 10 C), the capacity of the conventional battery is less than 50% of the original capacity measured at 0.5 C rate.

Example 2: Sulfonation of Electrically Non-Conducting Polymers

(60) Polytetrafluoroethylene (PTFE), polysulfone (PSf), poly (ether ether ketone) (PEEK), polyimide (PI), and styrene-butadiene copolymers (SB) were separately immersed in a concentrated sulfuric acid (95%+5% water) at 65-90° C. for 4-48 hours to obtain sulfonated polymers. These sulfonated polymers were found to be electrically insulating (<10.sup.−8 S/cm), but lithium ion-conducting (typically 3×10.sup.−5 S/cm-4.5×10.sup.−3 S/cm, depending on the degree of sulfonation).

(61) These highly sulfonated polymers, along with some desired amounts of baking soda as a blowing agent, were dissolved in water to form solutions, which were cast to form thin films onto a glass substrate and heated at 100° C.-250° C. for 0.3 to 5 minutes to produce porous structures. In one additional sample, graphene oxide sheets (graphene/polymer ratio= 1/10) were added to the sulfonated PEEK/baking soda solution to form a slurry, which was cast, dried, and heat-treated at 300° C. for 5 minutes to obtain a graphene-enhanced S-PEEK foam structure that was both electron-conducting and lithium ion-conducting. All these foamed structures were separately impregnated with lithium aniline sulfonate or lithium sulfate to form lithium ion reservoir layers.

Example 3: Preparation of Graphene Oxide Sheets (GO) and Reduced Graphene Oxide (RGO) Foam

(62) Chopped graphite fibers with an average diameter of 12 μm and natural graphite particles were separately used as a starting material, which was immersed in a mixture of concentrated sulfuric acid, nitric acid, and potassium permanganate (as the chemical intercalate and oxidizer) to prepare graphite intercalation compounds (GICs). The starting material was first dried in a vacuum oven for 24 h at 80° C. Then, a mixture of concentrated sulfuric acid, fuming nitric acid, and potassium permanganate (at a weight ratio of 4:1:0.05) was slowly added, under appropriate cooling and stirring, to a three-neck flask containing fiber segments. After 5-16 hours of reaction, the acid-treated graphite fibers or natural graphite particles were filtered and washed thoroughly with deionized water until the pH level of the solution reached 6. After being dried at 100° C. overnight, the resulting graphite intercalation compound (GIC) or graphite oxide fiber was re-dispersed in water and/or alcohol to form a slurry.

(63) In one sample, five grams of the graphite oxide fibers were mixed with 2,000 ml alcohol solution consisting of alcohol and distilled water with a ratio of 15:85 to obtain a slurry mass. Then, the mixture slurry was subjected to ultrasonic irradiation with a power of 200 W for various lengths of time. After 20 minutes of sonication, GO fibers were effectively exfoliated and separated into thin graphene oxide sheets with oxygen content of approximately 23%-31% by weight. The resulting suspension contains GO sheets being suspended in water. A chemical blowing agent (hydrazo dicarbonamide) was added to the suspension just prior to casting.

(64) The resulting suspension was then cast onto a stainless steel plate. A wiper was used to exert shear stresses at a high shearing rate, inducing GO sheet orientations. The wet GO suspension was then dried. For making a graphene foam specimen, the GO suspension was then subjected to heat treatments that typically involve an initial thermal reduction temperature of 80° C.-350° C. for 1-8 hours, followed by heat-treating at a second temperature of 1,500° C.-2,850° C. for 0.5 to 5 hours. We have found it essential to apply a compressive stress to the sample while being subjected to the first heat treatment. This compress stress seems to have helped maintain good contacts between the graphene sheets so that chemical merging and linking between graphene sheets can occur while pores are being formed. Without such a compressive stress, the heat-treated sample was typically excessively porous with constituent graphene sheets in the pore walls being very poorly oriented and incapable of chemical merging and linking with one another. As a result, the thermal conductivity, electrical conductivity, and mechanical strength of the graphene foam were compromised.

(65) The resulting graphene foam structures were then separately dipped in several lithium ion-capturing species in a liquid state, including sodium 4-methylbenzenesulfonate, sodium aniline sulfonate, sodium sulfate, sodium phosphate, and an ionic liquid having a tetra-alkylimidazolium cation and a BF.sub.4.sup.− anion, to prepare various lithium ion reservoir layers.

Example 4: Preparation of Pristine Graphene Foam (0% Oxygen)

(66) Recognizing the possibility of the high defect population in GO sheets acting to reduce the conductivity of individual graphene plane, we decided to study if the use of pristine graphene sheets (non-oxidized and oxygen-free, non-halogenated and halogen-free, etc.) can lead to a graphene foam having a higher thermal conductivity. Pristine graphene sheets were produced by using the direct ultrasonication or liquid-phase production process.

(67) In a typical procedure, five grams of graphite flakes, ground to approximately 20 μm or less in sizes, were dispersed in 1,000 mL of deionized water (containing 0.1% by weight of a dispersing agent, Zonyl® FSO from DuPont) to obtain a suspension. An ultrasonic energy level of 85 W (Branson S450 Ultrasonicator) was used for exfoliation, separation, and size reduction of graphene sheets for a period of 15 minutes to 2 hours. The resulting graphene sheets are pristine graphene that have never been oxidized and are oxygen-free and relatively defect-free. There are no other non-carbon elements.

(68) Various amounts (1%-30% by weight relative to graphene material) of chemical bowing agents (N,N-dinitroso pentamethylene tetramine or 4,4′-oxybis (benzenesulfonyl hydrazide) were added to a suspension containing pristine graphene sheets and a surfactant. The suspension was then cast onto a glass surface using a doctor's blade to exert shear stresses, inducing graphene sheet orientations. Several samples were cast, including one that was made using CO.sub.2 as a physical blowing agent introduced into the suspension just prior to casting). The resulting graphene suspension shapes, after removal of liquid, have a thickness that can be varied from approximately 0.1 mm to 50 mm.

(69) The graphene shapes were then subjected to heat treatments that involve an initial (first) thermal reduction temperature of 80° C.-1,500° C. for 1-5 hours. This first heat treatment generated a graphene foam structure. Some of the pristine foam samples were then subjected to a second temperature of 1,500° C.-2,850° C. to further perfect the graphene foam structure (re-graphitized to become more ordered or having a higher degree of crystallinity). These foam structures were used as a framework porous structure for accommodating lithium ion-capturing species.

Example 5: Lithium Ion-Conducting Polymer-Based Porous Structures

(70) Another group of presently invented lithium ion-conducting framework porous structures to retain lithium ion-capturing species therein typically comprises a mixture of a conventional lithium ion-conducting electrolyte polymer (e.g. PEO, PPO, etc.) and a sulfonated polymer, As shown in FIG. 2, the lithium ion conductivity values of a polymer mixture containing a conventional solid electrolyte polymer (PEO or PPO) and a sulfonated polymer exhibit unexpected synergistic effect. Some electron-conducting fillers (e.g. carbon nanotubes (CNF), carbon nanofibers (CNT), carbon black (CB), expanded graphite flakes (EGF), etc.) were added into lithium ion-conducting polymers to make a material both electron-conducting and lithium ion-conducting. Such a material appears to be more effective in capturing lithium ions during the fast battery charge operations, retaining more lithium ions in the resulting reservoir and continuing to send lithium ions into the anode layer even after the external charger unit is switched off.

(71) TABLE-US-00001 TABLE 2 Lithium ion conductivity of various conducting framework porous structure materials. Conducting Lithium- CNTs or conducting carbon polymer Li-ion Sample fibers (CF), (non-sulfonated conductivity No. etc. particles polymer) (S/cm) D1 CNT + CB PEO 1.1 × 10.sup.−4 to (15-85% by wt.) 8.5 × 10.sup.−4 S/cm D2 CNF PEO 2.3 × 10.sup.−4 to (5-95% by wt.) 8.2 × 10.sup.−4 S/cm D3 EGF PEO 2.3 × 10.sup.−4 to 7.2 × 10.sup.−4 S/cm D4 CNF + EGF PAN 6.5 × 10.sup.−5 to 5.3 × 10.sup.−4 S/cm D5 CNF + PPO 6.8 × 10.sup.−5 to graphene 4.9 × 10.sup.−4 S/cm D6 CNT + PEO + S-PANi 5.9 × 10.sup.−4 to graphene 7.7 × 10.sup.−3 S/cm D7 CNT PEO + S-PSf 3.4 × 10.sup.−4 to 1.3 × 10.sup.−3 S/cm

Example 6: Preparation of MoS.SUB.2./RGO Hybrid Cathode Material for Li Metal Cells (GO=Graphene Oxide; RGO=Reduced Graphene Oxide)

(72) Ultra-thin MoS.sub.2/RGO hybrid was synthesized by a one-step solvothermal reaction of (NH.sub.4).sub.2MoS.sub.4 and hydrazine in an N, N-dimethylformamide (DMF) solution of graphene oxide (GO) at 200° C. In a typical procedure, 22 mg of (NH.sub.4).sub.2MoS.sub.4 was added to 10 mg of GO dispersed in 10 ml of DMF. The mixture was sonicated at room temperature for approximately 10 min until a clear and homogeneous solution was obtained. After that, 0.1 ml of N.sub.2H.sub.4.H.sub.2O was added. The reaction solution was further sonicated for 30 min before being transferred to a 40 mL Teflon-lined autoclave. The system was heated in an oven at 200° C. for 10 h. Product was collected by centrifugation at 8000 rpm for 5 min, washed with DI water and recollected by centrifugation. The washing step was repeated for at least 5 times to ensure that most DMF was removed. Finally, product was dried and made into a cathode.

(73) The cathode layer, coated on an Al foil, was combined with a porous separator, a lithium ion reservoir layer, and a lithium metal foil (supported by a Cu foil) to make a battery cell. The electrolyte used was a quasi-solid electrolyte (3.5 M of LiPF.sub.6 in PC-EC solvent mixture). The resulting battery was found to be highly fire resistant when nail-penetrated.

Example 7: Preparation of Graphene-Enabled Li.SUB.x.V.SUB.3.O.SUB.8 .Nanosheets as a Cathode for a Li-Ion Cell

(74) All chemicals used in this study were analytical grade and were used as received without further purification. V.sub.2O.sub.5 (99.6%, Alfa Aesar) and LiOH (99+%, Sigma-Aldrich) were used to prepare the precursor solution. Graphene oxide (GO, 1% w/v obtained from Taiwan Graphene Co., Taipei, Taiwan) was used as a structure modifier. First, V.sub.2O.sub.5 and LiOH in a stoichiometric V/Li ratio of 1:3 were dissolved in actively stirred de-ionized water at 50° C. until an aqueous solution of Li.sub.xV.sub.3O.sub.8 was formed. Then, GO suspension was added while stirring, and the resulting suspension was atomized and dried in an oven at 160° C. to produce the spherical composite particulates of GO/Li.sub.xV.sub.3O.sub.8 nanosheets and the sample was designated NLVO-1. Corresponding Li.sub.xV.sub.3O.sub.8 materials were obtained under comparable processing conditions, but without graphene oxide sheets. The sample was designated as LVO-2.

(75) The Nyquist plots obtained from electrical impedance tests show a semicircle in the high to medium frequency range, which describes the charge-transfer resistance for both electrodes. The intercept value is considered to represent the total electrical resistance offered by the electrolyte. The inclined line represents the Warburg impedance at low frequency, which indicates the diffusion of ions in the solid matrix. The values of Rct for the vanadium oxide alone and graphene-enhanced composite electrodes are about 50.0 and 350.0Ω for NLVO-1 and LVO-2, respectively. The Rct of the composite electrode is much smaller than that of the LVO electrode. Therefore, the presence of graphene (<2% by weight in this case) in the vanadium oxide composite has dramatically reduced the internal charge transfer resistance and improved the battery performance upon extended cycling. NLVO-1 was subsequently used in two Li-ion cells (one featuring a Li ion reservoir layer and the other not) for evaluation of the effect of a lithium ion reservoir layer on the maximum amount of charges that can be stored in the anode.

(76) The NLVO-based cathode material was formed into a cathode and then combined with a layer of lithiated natural graphite particles (as an anode), a lithium ion reservoir layer and a porous separator layer (Celgard 2400) to prepare a lithium-ion battery. A corresponding cell containing no lithium ion reservoir layer was also prepared for comparison purpose. The electrolyte was a conventional PEO gel electrolyte containing LiPF.sub.6 in PC-EC solvent.

(77) The capacity of both cells was designed to be approximately 500 mAh in these two pouch cells. The actual charge storage capacity values of these two cells as a function of the charging C rates are summarized in FIG. 3, which clearly demonstrates the surprising effectiveness of the presently invented lithium ion reservoir approach to maintaining a high capacity at very high C rates.

Example 8: Relatively Fast-Chargeable Li—S Batteries

(78) The cathode electrode was prepared following the following procedure. The electrochemical deposition of sulfur (S) was conducted before the cathode active layer was incorporated into a lithium-sulfur battery cell (Li—S). The anode, the electrolyte, and the integral layer of porous graphene structure (serving as a cathode layer) are positioned in an external container outside of a lithium-sulfur cell. The needed apparatus was similar to an electroplating system, which is well-known in the art.

(79) In a typical procedure, a metal polysulfide (Li.sub.2S.sub.9 and Nai.sub.2S.sub.6) was dissolved in a solvent (e.g. mixture of DOL/DME at a volume ratio from 1:3 to 3:1) to form an electrolyte solution. The electrolyte solution was then poured into a chamber or reactor under a dry and controlled atmosphere condition (e.g. He or Nitrogen gas). A metal foil was used as the anode and a layer of the porous graphene foam structure as the cathode; both being immersed in the electrolyte solution. This configuration constitutes an electrochemical deposition system. The step of electrochemically depositing nanoscaled sulfur particles or coating on the graphene surfaces was conducted at a current density preferably in the range from 1 mA/g to 10 A/g, based on the layer weight of the porous graphene structure.

(80) The chemical reactions that occurred in this reactor may be represented by the following equation: M.sub.xS.sub.y.fwdarw.M.sub.xS.sub.y-z+zS (typically z=1-4). Quite surprisingly, the precipitated S is preferentially nucleated and grown on massive graphene surfaces to form nanoscaled coating or nanoparticles. The coating thickness or particle diameter and the amount of S coating/particles was controlled by the specific surface area, electrochemical reaction current density, temperature and time. In general, a lower current density and lower reaction temperature lead to a more uniform distribution of S and the reactions are easier to control. A longer reaction time leads to a larger amount of S deposited on graphene surfaces and the reaction is ceased when the sulfur source is consumed or when a desired amount of S is deposited.

(81) Several Li—S cells were produced wherein lithium metal foil was used as an anode active material and lithium trifluoromethane-sulfonimide (LiTFSI), dissolved in 1,3-dioxolane (DOL), was used as the electrolyte. In a first group of Li—S cells, a lithium ion reservoir layer obtained in Example 1 was implemented between a porous PE-PP separator and a lithium foil anode layer. In a second group of Li—S cells, graphene-reinforced sulfonated PEEK porous framework structure-based lithium ion reservoir (containing lithium aniline sulfonate or lithium phosphate as the lithium ion-capturing species), prepared in Example 2 was implemented between the Li metal anode and the porous separator. Baseline Li—S cells containing no lithium ion reservoir were also prepared and tested for comparison.

(82) It was observed that, the implementation of a lithium ion reservoir between the Li foil anode layer and the porous separator layer makes the resulting lithium-sulfur batteries fast-charged at a rate of 5 C to 15 C with only a 12-17% capacity reduction as compared to the same Li—S battery measured at a rate of 0.5 C. In contrast, when recharged at a high C rate (e.g. 10 C), the capacity of the baseline battery is reduced to become less than 50% of the original capacity measured at 0.5 C rate.

(83) The discharge capacity values of two Li—S cells (each featuring a Li foil as the anode active material and graphene-supported sulfur as the cathode active material) are plotted as a function of the number of charge/discharge cycles (FIG. 4). One cell contains a lithium ion reservoir disposed between the Li metal anode and the separator, but the other cell does not have such a reservoir. It is quite unexpected to observe that the implementation of such a lithium ion reservoir layer also results in a significantly more stable cycling behavior. Examination of post-cycling specimens led to the observation of a significant amount of dead lithium particles separated from the lithium foil anode of the cell containing no lithium ion reservoir. In contrast, the lithium metal anode surface of the cell featuring a lithium ion reservoir appeared relatively smooth and very few dead Li particles were observed. Such a reservoir layer seems capable of helping to stabilize the lithium metal-electrolyte interface zone and prevent dendrite formation, leading to a much longer cycle-life for a safer rechargeable lithium metal battery. Such a lithium ion reservoir strategy also enables the normally slow-charging lithium metal battery (including Li—S cell) to become fast chargeable.